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CN1175939A - Method for distilling alcohols - Google Patents

Method for distilling alcohols Download PDF

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Publication number
CN1175939A
CN1175939A CN96192097A CN96192097A CN1175939A CN 1175939 A CN1175939 A CN 1175939A CN 96192097 A CN96192097 A CN 96192097A CN 96192097 A CN96192097 A CN 96192097A CN 1175939 A CN1175939 A CN 1175939A
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CN
China
Prior art keywords
alcohol
weight
alkali metal
ethylhexyl alcohol
ethylhexyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN96192097A
Other languages
Chinese (zh)
Other versions
CN1074403C (en
Inventor
W·兹格泽尔斯基
P·拉普
K·沙拉普斯基
W·吉克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oxhey LLC
Serra nice chemical (Europe) Ltd.
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of CN1175939A publication Critical patent/CN1175939A/en
Application granted granted Critical
Publication of CN1074403C publication Critical patent/CN1074403C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method of distillatory purification of C3-C10 alcohols wherein the alcohols are distilled at 150 to 200 DEG C in the presence of 10 to 1000 ppm hydroxide alkali.

Description

The method of distilling alcohols
Aliphatics C 3-C 10-alcohol, such as propyl carbinol, particularly 2-Ethylhexyl Alcohol has very high economic worth.These pure preferred manufacturing procedure are hydrogenation of olefins formylations, afterwards with the aldehyde intermediate hydrogenation that forms (for example: propylene → just/isobutyric aldehyde → just/isopropylcarbinol) or by the aldolization (aldolization) of straight chain alkanoic (for example: butyraldehyde-n → 2-ethyl hexenal → 2-Ethylhexyl Alcohol) obtain the hydrogenation then of corresponding unsaturated aldehyde.General introduction sees as the industrial chemistry encyclopaedia that Ullmann showed: " alcohol, aliphatics " (A1 volume), " 2-Ethylhexyl Alcohol " (A10 volume) reaches " butanols " (A4 volume).
Except as solvent, propyl carbinol also can be used for paint and paint field in principle and is used to prepare carboxylicesters, particularly n-butyl acrylate and n-butyl phthalate (DBP).
Require the alcohols component of 2-Ethylhexyl Alcohol in principle as preparation phthalic acid two (2-ethylhexyl) ester (DEHP) and vinylformic acid (2-ethylhexyl) ester.
--prepare acrylate especially--using high purity alcohol for these Application Areass is the sin qua non.In the industrial preparation of alcohol, all carry out purifying by the multistage fractionation.In this case, alcohol will be exposed to thermal stresses following a few hours, uses 150-200 ℃ bottom temp usually.Therefore, at distillation aliphatics C 3-C 10-alcohol can produce corresponding aldehyde cut during such as butanols and 2-Ethylhexyl Alcohol, and it separates cost under the used normal condition in technology very high.
Therefore the objective of the invention is to find a kind of C that does not have these shortcomings 3-C 10The distillating method of-alcohol.
Surprisingly, we find to add the generation that the small amount of alkali metal hydroxides can suppress corresponding aldehyde in the still-process, and the aldehyde that has existed even also eliminated.
Therefore the present invention relates to a kind of by distillation purifying C 3-C 10The method of-alcohol, it is included under the condition that the alkali metal hydroxide of 10-1000ppm exists distills alcohol at 150-200 ℃.
C 3-C 10-alcohol can be straight chain or branching.The C of used particularly important for method of the present invention 3-C 10-alcohol is propyl carbinol and 2-Ethylhexyl Alcohol.
Preferred KOH of used alkali metal hydroxide or NaOH.The amount of alkali metal hydroxide is generally 10-1000ppm, preferred 10-200ppm, and every kind of situation all is that the amount in used alcohol is a base.Preferred alkali metal hydroxide adds with the form of the aqueous solution.
If use distillation tower in the distillation, 20-80 layer column plate arranged usually.
Shown in following embodiment, add that alkali metal hydroxide reduces usually greatly or even stoped the formation of aldehyde in the pure still-process fully, and the obvious minimizing of other unwanted side reaction or pure content does not take place.It usually is already present aldehyde even also eliminated in the used alcohol.
In an embodiment, term " low-boiler " refers to and does not contain 2-ethyl hexanal and the boiling point component than 2-Ethylhexyl Alcohol obvious low (low 20-40 ℃ at least), this component thereby can promptly separate by distillation.Similarly, term " high boiling compound " refers to and does not contain 2-ethyl hexanal and the boiling point component than the obvious height of 2-Ethylhexyl Alcohol (high at least 20-40 ℃), this component thereby can promptly separate by distillation.
The comparative example 1:
The 2-Ethylhexyl Alcohol that will contain 60ppm (0.006% weight) 2-ethyl hexanal heated 1 hour down at 180 ℃ under the situation that does not add alkali metal hydroxide.After 10,30 and 60 minutes, to every kind of situation sampling analysis.The results are shown in Table 1.After 60 minutes, 2-ethyl hexanal content is 140ppm (0.014% weight).
Embodiment 1:
According to comparative example 1 operation, different is added the KOH of 50ppm in 2-Ethylhexyl Alcohol before beginning to heat.The result also sees Table 1.After 30 minutes, 2-ethyl hexanal content is 0.001% weight, under the analyzing and testing limit.Table 1
Initial substance before the beginning Time after comparative example's (not adding alkali metal hydroxide) beginning Time after embodiment 1 (50ppm KOH) beginning
10 minutes 30 minutes 60 minutes 10 minutes 30 minutes 60 minutes
Low-boiler (% weight) ??0.216 ??0.212 ??0.211 ??0.212 ??0.208 ??0.209 ??0.207
2-ethyl hexanal (% weight) ??0.006 ??0.011 ??0.013 ??0.014 ??0.002 ??＜0.001 ??＜0.001
2-Ethylhexyl Alcohol (% weight) ??99.646 ??99.644 ??99.643 ??99.640 ??99.616 ??99.616 ??99.616
High boiling compound (% weight) ??0.132 ??0.133 ??0.133 ??0.134 ??0.174 ??0.175 ??0.177
The comparative example 2:
The 2-Ethylhexyl Alcohol of the following composition of 663g (% weight) uses in 2 liters distilling flask of a laboratory packed tower of having filled the high 3mmVA steel of 1m spiral.
Low-boiler 0.099
2-ethyl hexanal 0.001
2-Ethylhexyl Alcohol 99.770
High boiling compound 0.130
At pressure tower is that 100 millibars and recurrence rate are that the 5th kind of cut of every kind of 130g of four kinds of cuts and 65g taken overhead out under 118 ℃ under 3: 1 the situation.Study each cut with vapour phase chromatography.Table 2
Cut ????1 ????2 ????3 ????4 ????5
Low-boiler (% weight) ??0.010 ??0.006 ??0.003 ??0.011 ??0.008
2-ethyl hexanal (% weight) ??0.013 ??0.009 ??0.008 ??0.010 ??0.011
2-Ethylhexyl Alcohol (% weight) ??99.863 ??99.980 ??99.986 ??99.975 ??99.977
High boiling compound (% weight) ??0.114 ??0.005 ??0.003 ??0.004 ??0.004
The content of 2-ethyl hexanal is under the analyzing and testing limit in the distillation residue (78g).
Embodiment 2
According to comparative example 2 operation, difference is to add the KOH aqueous solution of 66mg50% concentration in 2-Ethylhexyl Alcohol before beginning to distill.Study each cut with vapour phase chromatography again.
Table 3
Cut ????1 ????2 ????3 ????4 ????5
Low-boiler (% weight) ??0.010 ??0.006 ??0.003 ??0.011 ??0.008
2-ethyl hexanal (% weight) ??0.003 ??0.002 ??0.001 ??0.001 ??0.001
2-Ethylhexyl Alcohol (% weight) ??99.863 ??99.987 ??99.993 ??99?984 ??99.987
High boiling compound (% weight) ??0.124 ??0.005 ??0.003 ??0.004 ??0.004
2-ethyl hexanal content is under the analyzing and testing limit in the distillation residue (78g).

Claims (3)

1. one kind is passed through distillation purifying C 3-C 10The method of alcohol is included under the condition that the 10-1000ppm alkali metal hydroxide exists at 150-200 ℃ of distilling alcohols.
2. method as claimed in claim 1, wherein, propyl carbinol or 2-Ethylhexyl Alcohol are as C 3-C 10Alcohol.
3. as the method for claim 1 or 2, distilling alcohols under the condition that the 10-200ppm alkali metal hydroxide exists wherein.
CN96192097A 1995-02-23 1996-02-14 Method for distilling alcohols Expired - Fee Related CN1074403C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19506280.9 1995-02-23
DE19506280A DE19506280A1 (en) 1995-02-23 1995-02-23 Process for the distillation of alcohols

Publications (2)

Publication Number Publication Date
CN1175939A true CN1175939A (en) 1998-03-11
CN1074403C CN1074403C (en) 2001-11-07

Family

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CN96192097A Expired - Fee Related CN1074403C (en) 1995-02-23 1996-02-14 Method for distilling alcohols

Country Status (21)

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US (1) US6117277A (en)
EP (1) EP0869936B1 (en)
JP (1) JP3806146B2 (en)
KR (1) KR100410705B1 (en)
CN (1) CN1074403C (en)
AT (1) ATE195503T1 (en)
AU (1) AU702668B2 (en)
BR (1) BR9607105A (en)
CA (1) CA2213614C (en)
DE (2) DE19506280A1 (en)
DK (1) DK0869936T3 (en)
ES (1) ES2151147T3 (en)
FI (1) FI973433A (en)
IN (1) IN186279B (en)
MX (1) MX9706195A (en)
MY (1) MY115717A (en)
PL (1) PL182127B1 (en)
PT (1) PT869936E (en)
RO (1) RO117845B1 (en)
WO (1) WO1996026173A1 (en)
ZA (1) ZA961408B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103987852A (en) * 2011-10-14 2014-08-13 东丽株式会社 Process for producing 2,3-butanediol
CN105001046A (en) * 2015-07-09 2015-10-28 武汉工程大学 Nonyl alcohol synthesis process

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19809493A1 (en) * 1998-03-05 1999-09-09 Basf Ag Process for the distillation of mixtures containing butanediol
DE10024542A1 (en) 2000-05-18 2001-11-22 Basf Ag Production of saturated 3-20C alcohols uses a hydrogenation catalyst bed in the presence of a salt-like base in the reactant feed containing an anion of an acid having a pKa of greater than 2
JP2002047225A (en) * 2000-07-27 2002-02-12 Mitsubishi Gas Chem Co Inc Method for distilling polycyclic diol compounds
GR1003703B (en) * 2000-12-27 2001-10-23 Celanese Chemicals Europe Gmbh Method for distilling alcohols
DE10161597B4 (en) * 2001-12-14 2005-10-20 Celanese Chem Europe Gmbh Process for the purification of alicyclic alcohols
DE10252173B3 (en) * 2002-11-09 2004-06-03 Celanese Chemicals Europe Gmbh Process for the recovery of aliphatic C3-C10 alcohols from high boilers
CN101765578A (en) * 2007-07-30 2010-06-30 陶氏环球技术公司 C 6-C 16The process for purification of aliphatic diol
KR101191112B1 (en) 2009-03-19 2012-10-15 주식회사 엘지화학 Dividing wall column for production of high purity 2-ethylhexanol and distillating method using thereof
EP2607341B1 (en) * 2009-12-24 2015-11-18 Oxea Bishop LLC Trimethylolpropane color improvement
CA2878966A1 (en) * 2012-07-26 2014-01-30 Butamax Advanced Biofuels Llc Butanol purification
EP2947065B1 (en) 2013-01-16 2020-04-22 LG Chem, Ltd. Device and process for preparing an octanol
RU2667527C2 (en) * 2013-07-02 2018-09-21 Басф Се Method for preparation of 3-heptanol from mixture containing 2-ehthylhexanal and 3-heptyl formate
JP6088922B2 (en) * 2013-07-03 2017-03-01 花王株式会社 Method for producing Gerve alcohol
US9512054B2 (en) 2015-02-10 2016-12-06 Eastman Chemical Company Method for making a high purity alcohol

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US2626284A (en) * 1949-09-17 1953-01-20 Standard Oil Dev Co Aqueous caustic treat of iso-octyl alcohol
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AT283295B (en) * 1967-12-20 1970-07-27 Basf Ag Process for the production of butanols
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DD228542A1 (en) * 1984-11-09 1985-10-16 Leuna Werke Veb PROCESS FOR RECOVERING PROPANOL-1
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103987852A (en) * 2011-10-14 2014-08-13 东丽株式会社 Process for producing 2,3-butanediol
CN103987852B (en) * 2011-10-14 2017-02-15 东丽株式会社 Process for producing 2,3-butanediol
CN105001046A (en) * 2015-07-09 2015-10-28 武汉工程大学 Nonyl alcohol synthesis process

Also Published As

Publication number Publication date
ES2151147T3 (en) 2000-12-16
MX9706195A (en) 1997-11-29
ATE195503T1 (en) 2000-09-15
DK0869936T3 (en) 2000-11-20
PL321896A1 (en) 1997-12-22
FI973433A0 (en) 1997-08-21
PT869936E (en) 2000-12-29
AU4876096A (en) 1996-09-11
EP0869936B1 (en) 2000-08-16
ZA961408B (en) 1997-11-24
JP3806146B2 (en) 2006-08-09
JPH11500437A (en) 1999-01-12
DE19506280A1 (en) 1996-08-29
AU702668B2 (en) 1999-02-25
MY115717A (en) 2003-08-30
IN186279B (en) 2001-07-28
DE59605765D1 (en) 2000-09-21
KR100410705B1 (en) 2004-03-30
FI973433A (en) 1997-08-21
RO117845B1 (en) 2002-08-30
CN1074403C (en) 2001-11-07
US6117277A (en) 2000-09-12
EP0869936A1 (en) 1998-10-14
KR19980702375A (en) 1998-07-15
BR9607105A (en) 1997-11-04
PL182127B1 (en) 2001-11-30
CA2213614C (en) 2001-07-03
WO1996026173A1 (en) 1996-08-29
CA2213614A1 (en) 1996-08-29

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Granted publication date: 20011107